Liquid compositions containing N-alkyl ammonium acetonitrile salts

ABSTRACT

The invention provides liquid cleaning or bleaching compositions containing compounds having the structure of Formula I ##STR1## wherein A is a saturated ring formed by five atoms in addition to the N 1  atom, the five saturated ring atoms being four carbon atoms and a heteroatom, the substituent R 1  bound to the N 1  atom of the Formula I structure including either (a) a C 1-24  alkyl or alkoxylated alkyl where the alkoxy is C 2-4 , (b) a C 4-24  cycloalkyl, (c) a C 7-24  alkaryl, (d) a repeating or nonrepeating alkoxy or alkoxylated alcohol, where the alkoxy unit is C 2-4 , or (e) --CR 2  R 3  CN where R 2  and R 3  are each H, a C 1-24  alkyl, cycloalkyl, or alkaryl, or a repeating or nonrepeating alkoxyl or alkoxylated alcohol where the alkoxy unit is C 2-4 , the R 2  and R 3  substituents are each H, a C 1-24  alkyl, cycloalkyl, or alkaryl, or a repeating or nonrepeating alkoxyl or alkoxylated alcohol where the alkoxy unit is C 2-4 , and wherein Y is a generally anionic counterion and Z is in the range of 0 to 10. Additional, adjunct materials commonly found in liquid cleaning and bleaching compositions can be added.

This application is a continuation in part of Ser. No. 08/475,292, filedJun. 7, 1995, now U.S. Pat. No. 5,739,327 entitled "N-ALKYL AMMONIUMACETONITRILE BLEACH ACTIVATORS," inventors Arbogast et al., of commonassignment herewith.

FIELD OF THE INVENTION

The present invention generally relates to N-alkyl ammonium acetonitrilecompounds in a liquid matrix, and particularly liquid compositionscontaining a source of active oxygen useful in applications such asbleaching and cleaning.

BACKGROUND OF THE INVENTION

Peroxy compounds are effective bleaching agents, and compositionsincluding mono- or di-peroxyacid compounds are useful for industrial orhome cleaning or laundering operations. For example, U.S. Pat. No.3,996,152, issued Dec. 7, 1976, inventors Edwards et al., disclosesbleaching compositions including peroxygen compounds such asdiperazelaic acid and diperisophthalic acid.

Peroxyacids (also known as "peracids") have typically been prepared bythe reaction of carboxylic acids with hydrogen peroxide in the presenceof sulfuric acid. For example, U.S. Pat. No. 4,337,213, inventorsMarynowski et al., issued Jun. 29, 1982, discloses a method for makingdiperoxyacids in which a high solids throughput may be achieved.

However, bleaching products containing peroxyacid compounds tend to losebleaching activity during storage, due to decomposition of theperoxyacid. The relative instability of peroxyacid can present a problemof storage stability for compositions consisting of or includingperoxyacids.

One approach to the problem of reduced bleaching activity of peroxyacidcompositions has been to include activators of peroxyacids. U.S. Pat.No. 4,772,290, issued Sep. 20, 1988, inventors Mitchell et al., and U.S.Pat. No. 4,900,469, issued Feb. 13, 1990, inventors Farr et al., both ofwhich are of common assignment herewith, disclose stable organic bleachactivators suspended in a liquid hydrogen peroxide matrix.

U.S. Pat. No. 4,915,863, issued Apr. 10, 1990, inventors Aoyagi et al.,discloses compounds said to be peracid precursors that have nitrilemoieties. U.S. Pat. No. 5,236,616, issued Aug. 17, 1993, inventors Oakeset al., discloses compounds said to be cationic peroxyacid precursorsthat have nitrile moieties. These nitrile containing activators do notcontain a leaving group, such as found in ester-type bleach activators,but instead include a quaternary ammonium group suggested as activatingthe nitrile and said, upon hydrolysis in the presence of hydrogenperoxide, to generate a peroxyimidic acid as bleaching species. TheAoyagi et al. activators include an aromatic ring, which tends to causefabric yellowing.

German patent application DE OS 44 312 12, published Mar. 7, 1996,describes production of quaternized glycinonitriles in the form ofstable aqueous solutions.

In the parent application, Ser. No. 08/475,292, now U.S. Pat. No.5,739,327 N-methylmorpholinium acetonitrile methylsulfate ("MMA") isnoted as being of special interest. The MMA is useful as an activator inbleaching applications when combined with a source of active oxygen.These compounds and related ones, however, may be incorporated intoliquid formulations, both with and without a source of active oxygen.

SUMMARY OF THE INVENTION

The present invention provides liquid cleaning or bleaching compositionscomprising compounds having the structure of Formula I

FORMULA I ##STR2## wherein A is a saturated ring formed by five atoms inaddition to the N₁ atom, the five saturated ring atoms being four carbonatoms and a heteroatom, the substituent R₁ bound to the N₁ atom of theFormula I structure including either (a) a C₁₋₂₄ alkyl or alkoxylatedalkyl where the alkoxy is C₂₋₄, (b) a C₄₋₂₄ cycloalkyl, (c) a C₇₋₂₄alkaryl, (d) a repeating or nonrepeating alkoxy or alkoxylated alcohol,where the alkoxy unit is C₂₋₄, or (e) --CR₂ R₃ C.tbd.N where R₂ and R₃are each H, a C₁₋₂₄ alkyl, cycloalkyl, or alkaryl, or a repeating ornonrepeating alkoxyl or alkoxylated alcohol where the alkoxy unit isC₂₋₄, the R₂ and R₃ substituents are each H, a C₁₋₂₄ alkyl, cycloalkyl,or alkaryl, or a repeating or nonrepeating alkoxyl or alkoxylatedalcohol where the alkoxy unit is C₂₋₄, and wherein Y is a generallyanionic counterion and Z is in the range of 0 to 10.

The Formula I compounds have a quaternary nitrogen atom (N₁), requiringthe presence of at least one counterion (Y) to be associated therewith.Counterions for the inventive salts include both organic and inorganicanions, preferably alkylsulfate, especially methylsulfate, sulfate orbisulfate, tosylate and mesylate, and chloride, bromide, and nitrate.Especially preferred are methylsulfate, sulfate, bisulfate, tosylate andmixtures thereof, which have been found to result in surprisinglyadvantageous properties for the novel Formula I compounds. Additionally,although Y has been indicated in Formula I to be monovalent, in fact, itcan be multivalent. As an example, when Y is sulfate, the counterion isdivalent. Accordingly, these inventive salts are particularly wellsuited to bleaching and cleaning compositions.

The novel compounds with the Formula I structure are particularly usefulwhen formulated as compositions that include a source of active oxygen,and these compositions provide excellent bleaching in alkalinesolutions.

Preferred embodiments of the invention include lower alkyls substitutedat the N₁, e.g. N-methyl morpholinium acetonitrile, N-ethyl morpholiniumacetonitrile, N-butyl morpholinium acetonitrile, which are illustratedby Formula II (with "n" preferably being 0 to 24 and where "Y" is one ofthe above described counterions).

FORMULA II ##STR3##

A particularly preferred embodiment of the invention are liquidcompositions containing N-methyl morpholinium acetonitrilemethylsulfate, sulfate, bisulfate salts (sometimes designated as,respectively, "MMAMS," "MMAS" or "MMABS," where "n" of Formula II is 0),or mixtures thereof, which have excellent stability, and which showexcellent bleaching and cleaning performance when formulated with asource of active oxygen in alkaline wash water. Tosylate salts are alsopreferred and would be designated as "MMATS."

When formulated with a source of active oxygen, compositions of theinvention are useful as or in home cleaning and laundry products, suchas bleaching additives, detergents, detergent boosters, detergents withbleach, bleaches, bleaching aids, dishwashing detergents, surface andmildew stain removers, and spot treatment products such as stainremovers, prewash and presoak laundry aids. Among the advantages derivedfrom compositions of the invention are improved cleaning, stain removal,spot removal, whitening, and brightening of treated articles.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 shows a graph depicting performance of a preferred embodiment ofthe invention formulated as a hard surface cleaner at various pH's.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The novel compounds used in the invention include certain nitriteshaving the structure illustrated by Formula I. The N₁ atom of theFormula I compound is part of a saturated ring, illustrated by "A" inFormula I.

FORMULA I ##STR4## This saturated ring of which N₁ is a part has fiveatoms in addition to N₁, with at least one heteroatom being in thesaturated ring in addition to the N₁, preferably wherein the heteroatomof the ring is an oxygen atom or a sulfur atom.

The N₁ atom shown in Formula I is N-acetonitrile substituted and alsoquaternized. Without being bound by theory, it is believed that theelectron withdrawing nature of the quaternary nitrogen may be increasedby being part of a saturated, heterocyclic ring and may also function toimprove the hydrophilic character of the oxidant.

A substituent R₁ will be bonded to the N₁ atom of the Formula Istructure and additionally a nitrile moiety (--CR₂ R₃ C.tbd.N) is bondedto the N₁ atom, where R₂ and R₃ are each H, a C₁₋₂₄ alkyl, cycloalkyl,or alkylaryl, or a repeating or nonrepeating alkoxyl or alkoxylatedalcohol where the alkoxy unit is C₂₋₄. The R₁ substituent may be a C₁₋₂₄alkyl or alkoxylated alkyl where the alkoxy is C₂₋₄, a C₄₋₂₄ cycloalkyl,a C₇₋₂₄ alkylaryl, a repeating or nonrepeating alkoxy or alkoxylatedalcohol, where the alkoxy unit is C₂₋₄, and illustrative such groupsare, for example, ##STR5## where j=1 to 24. The R₁ substituent may alsobe another --CR₂ R₃ C.tbd.N, and again R₂ and R₃ are each H, a C₁₋₂₄alkyl, cycloalkyl, or alkylaryl, or a repeating or nonrepeating alkoxylor alkoxylated alcohol where the alkoxy unit is C₂₋₄, and illustrativesuch groups are: ##STR6## where j=1 to 24.

Particularly preferred activator embodiments are illustrated by FormulaII (where "Y" is as earlier described and "n" is 0 to 24.

FORMULA II ##STR7##

Novel derivatives used in the liquid compositions of the inventioninclude peroxyimidic intermediates that are believed formed from thenovel nitrites in the presence of an active oxygen source. So formed,peroxyimidic derivatives typically would be short-lived intermediatesformed in situ when the nitrites of the invention interact with a sourceof hydrogen peroxide and where the reactive nitrile moiety forms aperoxyimidic acid. However, such peroxyimidic derivatives may also beprepared in situ by analogy to syntheses known in the art.

1. Counterions

Since compounds of the invention are typically quaternized, they willinclude at least one counterion (designated as "Y"), selected from awide variety of anionic counterions, especially alkylsulfate (e.g.,methylsulfate), sulfate or bisulfate, or mixtures thereof, mesylate andtosylate. In the copending parent application of which this is acontinuation-in-part, N-alkyl ammonium acetonitrile compounds aredisclosed as typically including such wide variety of counterions suchas chloride, bromide, nitrate, alkyl sulfate, and the like. There, thepreferred embodiment was described as N-methyl ammonium acetonitrilemethyl sulfate. In addition, in the present invention of sulfate orbisulfate salt may be produced from heated and acidified MMA (as methylsulfate). However, the sulfate and bisulfate salts appear to exist in anequilibrium, the predominance of one over the other dependent upon pH.Three preferred salts are illustrated by Formulas IIIA, IIIB and IIIC.

FORMULA III ##STR8## 2. Bleaching and Cleaning Compositions

Bleaching and cleaning compositions of the invention include the FormulaI nitrile salts as activator, together with a source of active oxygen.

The peroxide or active oxygen source for compositions of the inventionmay be selected from most preferably hydrogen peroxide, Caro's acid(peroxymonosulfuric acid), and then, as suspended particulate oxidants,the alkali metal and alkaline metal salts of percarbonate, perborate,persilicate and hydrogen peroxide adducts. Examples of hydrogen peroxideformulations suitable for use herein include those depicted in Mitchellet al., U.S. Pat. No. 4,900,468, Farr et al., U.S. Pat. No. 5,180,514and Baker et al., U.S. Pat. No. 4,764,302, all of common assignment andall of which are incorporated herein by reference. Where sodiumpercarbonate, sodium perborate mono- and tetrahydrate, are utilized inaqueous formulations, it is most preferable to suspend them in suchaqueous formulations, along with stabilizers. Exemplary of these systemsare Peterson et al., U.S. Pat. No. 5,464,552, Published European PatentApplications EP 294 904 and EP 293 040, incorporated herein byreference. Other peroxygen sources may be possible, such asmonopersulfates and monoperphosphates, or their equivalent aqueousforms, such as monopersulfuric acid, known in the trade as Caro's acidor Caroate®, a product of BASF AG, Germany; and poorly soluble oxidants,such as alkaline earth peroxides, for example, Gray et al., U.S. Pat.Nos. 4,891,147 and 5,019,189, both of which are incorporated herein byreference. Alternatively, the formulations of the invention may beessentially nonaqueous. These nonaqueous formulations will have anonaqueous liquid as the continuous phase, such as nonionic surfactant,or nonaqueous organic solvents such as glycol ethers, hydrocarbons,acids, alcohols, and the like. A nonaqueous formulation would beexpected to be highly chemically stable because bleach activators suchas MMA are less likely to be hydrolyzed in the nonaqueous continuousmatrix. Exemplary nonaqueous formulations are depicted in Peterson etal., U.S. Pat. No. 4,874,537, and Van Buskirk et al., U.S. Pat. No.5,415,796, both of which are incorporated herein by reference.

The range of peroxide to activator is preferably determined as a molarratio of peroxide to activator. Thus, the range of peroxide to eachactivator is a molar ratio of from about 0.1:1 to 100:1, more preferablyabout 1:1 to 10:1 and most preferably about 2:1 to 8:1. This peracidactivator/peroxide composition should provide about 0.5 to 100 ppm A.O.,more preferably about 1 to 50 ppm peracid A.O. (active oxygen), and mostpreferably about 1 to 20 ppm peracid A.O., in aqueous media for typicallaundry applications. Formulations intended for hard surface cleaningwill more typically have peracid activator/peroxide providing from about0.5 to 500,000 ppm A.O., more preferably about 1 to 20,000 ppm peracidA.O., and most preferably about 1 to 10,000 ppm peracid A.O.

However, one of the advantages of the inventive MMA compounds is thatthose tested have been found to be oxidatively stable when formulatedwith hydrogen peroxide, preferably at a low pH. This allows for greatflexibility when formulating liquid products since the MMA compounds donot necessarily need to be kept separate from the source of activeoxygen.

Compositions of the invention have been found to provide superiorbleaching (cleaning and stain removal) benefits on common laundry andhousehold stains.

3. Delivery Systems

The liquid compositions of the invention can take numerous desirableforms. For example, without limitation, these include macroemulsions,microemulsions, structured liquids, liquid crystals, vesicular systems,lamellar systems, suspensions, dispersions, gels, mulls and pastes.These liquid systems can be clear or translucent (such asmicroemulsions) to opaque. These liquid systems can either be cleaningliquids wherein the inventive compounds are present as potentiallyantimicrobial actives, or, where a source of peroxygen (active oxygen)is present, as a bleaching liquid, as well as detergents and detergentbleaches. They can also be either unitary systems, or multipledeliveries, such as, for example, a dual chamber container, one chambercontaining the inventive N-alkyl ammonium acetonitrile compounds with asource of active oxygen, while the other contains a solution includingactives sensitive to oxidation, for example, enzymes and fluorescentwhitening agents. An example of a container which can co-dispense thesetwo different liquid compositions is found in Beacham et al., U.S. Pat.No. 4,585,150, incorporated herein by reference; and an example of asystem where a dual delivery is depicted, with one part containing aliquid oxidant formulation, the other, a liquid with materials which aresensitive to oxidation, is found in Co-pending applications of Choy etal., Ser. Nos. 08/605,822 now U.S. Pat. No. 5,767,005, and 08/605,824,both filed Feb. 23, 1996, and both entitled "Composition and Apparatusfor Surface Cleaning," of common assignment, incorporated herein byreference. In the case of more viscous forms, such as gels, mulls orpastes, the continuous phase can be nonionic surfactants, and isexemplified by Kaufmann et al., U.S. Pat. Nos. 4,743,394 and 5,362,413,both of which are incorporated herein by reference.

The liquid compositions of this invention frequently contain varyingamounts of surfactants, which may act both as a cleaning activeingredient, but also to help disperse sparingly soluble materials in theliquid phase, or which may serve as the continuous phase in anessentially nonaqueous composition.

4. Surfactants

Surfactants with which the activators and active oxygen compositions maybe combined or admixed include linear ethoxylated alcohols, such asthose sold by Shell Chemical Company under the brand name Neodol. Othersuitable nonionic surfactants can include other linear ethoxylatedalcohols with an average length of 6 to 16 carbon atoms and averagingabout 2 to 20 moles of ethylene oxide per mole of alcohol; linear andbranched, primary and secondary ethoxylated, propoxylated alcohols withan average length of about 6 to 16 carbon atoms and averaging 0-10 molesof ethylene oxide and about 1 to 10 moles of propylene oxide per mole ofalcohol; linear and branched alkylphenoxy (polyethoxy) alcohols,otherwise known as ethoxylated alkylphenols, with an average chainlength of 8 to 16 carbon atoms and averaging 1.5 to 30 moles of ethyleneoxide per mole of alcohol; and mixtures thereof. Shell Chemical,Huntsman Chemical and Union Carbide are among the numerous producers ofthese surfactants.

Further suitable nonionic surfactants may include polyoxyethylenecarboxylic acid esters, fatty acid glycerol esters, fatty acid andethoxylated fatty acid alkanolamides, certain block copolymers ofpropylene oxide and ethylene oxide, and block polymers or propyleneoxide and ethylene oxide with propoxylated ethylene diamine. Alsoincluded are such semi-polar nonionic surfactants like amine oxides(such as Ammonyx from Stepan and Barlox from Lonza), phosphine oxides,sulfoxides and their ethoxylated derivatives.

Anionic surfactants may also be suitable. Examples of such anionicsurfactants may include the ammonium, substituted ammonium (e.g.,mono-di-, and triethanolammonium), alkali metal and alkaline earth metalsalts of C₆ -C₂₀ fatty acids and rosin acids, linear and branched alkylbenzene sulfonates, alkyl sulfates, alkyl ether sulfates, alkanesulfonates, alpha olefin sulfonates, hydroxyalkane sulfonates, fattyacid monoglyceride sulfates, alkyl glyceryl ether sulfates, acylsarcosinates and acyl N-methyltaurides.

Suitable cationic surfactants may include the quaternary ammoniumcompounds in which typically one of the groups linked to the nitrogenatom is a C₁₂ -C₁₈ alkyl group and the other three groups are shortchained alkyl groups which may bear inert substituents such as phenylgroups.

Suitable amphoteric and zwitterionic surfactants containing an anionicwater-solubilizing group, a cationic group or a hydrophobic organicgroup include amino carboxylic acids and their salts, amino dicarboxylicacids and their salts, alkyl-betaines, alkyl aminopropylbetaines,sulfobetaines, alkyl imidazolinium derivatives, certain quaternaryammonium compounds, certain quaternary phosphonium compounds and certaintertiary sulfonium compounds.

These and other types of surfactants are exemplified in McCutcheon'sEmulsifiers and Detergents (1994) and Kirk-Othmer Encyclopedia ofChemical Technology 3rd, Vol. 22, "Surfactants," pp. 332-432 (1983),both of which are incorporated herein by reference.

Other common detergent adjuncts may be added if a bleach or detergentbleach product is desired; See 6 below.

5. Source of Acid/Alkali

Compositions of the invention, when combined with a source of activeoxygen, preferably function for bleaching best at a neutral to alkalinepH, but are shelf stabilized best at an acidic pH. Thus, compositions ofthe invention preferably include a source of protons as an "acid sink."This can be achieved by having a mineral or organic acid present. Theseinclude, but are not limited to, mineral acids selected from phosphoric,sulfuric, hydrochloric, nitric, carbonic, boric, sulfamic, sulfurousacids and mixtures thereof; and organic acids selected from acetic,hydroxyacetic (glycolic), citric, succinic, maleic benzoic, oxalicacids, and mixtures thereof. It may also be possible to use the acidicforms of materials ordinarily viewed as hydrotropes, such as toluenesulfonic acid, xylene sulfonic acid, cumene sulfonic acid, and the like;and surfactants, such as alkylbenzene sulfonic acid (also known asHLAS), exemplary of which is dodecyl benzene sulfonic acid (See Choy etal., U.S. Pat. Nos. 4,759,867, 4,804,491 and 4,895,669, incorporatedherein by reference). However, the compositions of the invention canalso be pH adjusted for a variety of applications, such as when used asa mildew or other type of stain remover.

When the composition is ready for use as a laundry additive, it isespecially advantageous to have an amount of alkaline buffer presentsufficient to maintain a pH greater than about 6.0, more preferably inthe range of about 8.5 to about 10.5 for most effective bleaching, whenthe liquid formulation is dispensed into an aqueous wash system. As ahard surface cleaner, on the other hand, it may be useful to co-dispensethe alkaline buffer in a separate, preferably liquid, composition. Thesealkaline buffers include, but are not limited to, alkali metalhydroxides (sodium, lithium, potassium), ammonium hydroxide, alkalimetal ortho-, meta- and pyrophosphates, alkali metal silicates, alkalimetal tetraborates (penta- and decahydrates), alkali metal and ammoniumcarbonates, alkali metal and ammonium carbamates (See Garabedian, Jr.,et al., U.S. Pat. Nos. 5,523,024, 5,468,423, 5,437,807 and 5,252,245,all incorporated herein by reference), alkali metal and ammoniumpolyacrylates, alkali metal and ammonium succinates, alkali metal andammonium maleates and additional conjugate bases of weak organic acids,such as those mentioned hereinabove. Further, organic bases areincluded, such as, without limitation, ethanolamine, diethanolamine,triethanolamine, hydroxyamine, methylamine, dimethylamine andtrimethylamine. On the other hand, acidic hard surface cleaners arecertainly well known and preferred for use as bathroom cleaners. Thesetypes of cleaners therefore are acidified with the type of acidsdescribed hereinabove.

6. Additional Functional/Aesthetic Adjuncts

Other adjuncts (useful in cleaning and laundering applications) areoptionally included in the inventive compositions. Dyes includeanthraquinone and similar blue dyes. Pigments may also be used.Monastral colorants are also possible for inclusion. Brighteners orwhiteners, such as stilbene, styrene and styrylnaphthalene brighteners(fluorescent whitening agents), may be included. Fragrances used foraesthetic purposes are commercially available from Quest, Sozio,Firmenich, Dragoco, Bush Broke and Allen, Norda, International Flavorsand Fragrances and Givaudon. Stabilizers include hydrated salts, such asmagnesium sulfate, and boric acid.

In some of the compositions herein, adjuvants include (and areespecially preferred) a chelating agent or sequestrant, most preferably,an aminopolyphosphonate. These chelating agents assist in maintainingthe solution stability of the salt activators and active oxygen sourcein order to achieve optimum performance. In this manner, they are actingto chelate heavy metal ions, which cause catalyzed decomposition of the(believed) in situ formed peroxyimidic acids, although this is anon-binding theory of their action and not limiting.

The chelating agent is selected from a number of known agents which areeffective at chelating heavy metal ions. The chelating agent should beresistant to hydrolysis and rapid oxidation by oxidants. Preferably, itshould have an acid dissociation constant (pKa) of about 1-9, indicatingthat it dissociates at low pH's to enhance binding to metal cations.Acceptable amounts of the (optional) chelating agent range from 0-1,000,more preferably 5-500, most preferably 10-100 ppm chelating agent, inthe wash liquor. As a hard surface cleaner, however, it is preferred toadd amounts of the chelating agent form 0-100,000, more preferably5-50,000, and most preferably 10-10,000 ppm chelating agent.

The most preferred chelating agent is an aminopolyphosphonate, which iscommercially available under the trademark Dequest from MonsantoCompany. Examples thereof are Dequest 2000, 2041 and 2060. (See alsoBossu U.S. Pat. No. 4,473,507, column 12, line 63 through column 13,line 22, incorporated herein by reference.) A polyphosphonate, such asDequest 2010, is also suitable for use.

Other chelating agents, such as ethylenediaminetetraacetic acid (EDTA)and nitrilotriacetic acid (NTA) may also be suitable for use. Stillother new, preferred chelating agents are newpropylenediaminetetraacetates, such as Hampshire 1,3 PDTA, from W.R.Grace, and Chel DTPA 100#F, from Ciba Geigy A.G. Mixtures of theforegoing may be suitable.

Additional desirable adjuncts are enzymes (although it may be preferredto also include an enzyme stabilizer). Proteases are one especiallypreferred class of enzymes. They are preferably selected from alkalineproteases. The term "alkaline," refers to the pH at which the enzymes'activity is optimal. Alkaline proteases are available from a widevariety of sources, and are typically produced from variousmicroorganism (e.g., Bacillus subtilisis). Typical examples of alkalineproteases include Maxatase and Maxacal from International BioSynthetics,Alcalase, Savinase, and Esperase, all available from Novo Nordisk A/S.See also Stanislowski et al., U.S. Pat. No. 4,511,490, incorporatedherein by reference. Further suitable enzymes are amylases, which arecarbohydrate-hydrolyzing enzymes. It is also preferred to includemixtures of amylases and proteases. Suitable amylases include Rapidase,from Societe Rapidase, Milezyme from Miles Laboratory, and Maxamyl fromInternational BioSynthetics.

Still other suitable enzymes are cellulases, such as those described inTai, U.S. Pat. No. 4,479,881, Murata et al., U.S. Pat. No. 4,443,355,Barbesgaard et al., U.S. Pat. No. 4,435,307, and Ohya et al., U.S. Pat.No. 3,983,082, incorporated herein by reference.

Yet other suitable enzymes are lipases, such as those described inSilver, U.S. Pat. No. 3,950,277, Thom et al., U.S. Pat. No. 4,707,291,and Wiersema et al., U.S. Pat. Nos. 5,296,161 and 5,030,240, and Pouloseet al., U.S. Pat. No. 5,108,457, incorporated herein by reference.

The hydrolytic enzyme should be present in an amount of about 0.01-5%,more preferably about 0.01-3%, and most preferably about 0.1-2% byweight of the detergent. Mixtures of any of the foregoing hydrolases aredesirable, especially protease/amylase blends.

Some of the adjuncts, such as fluorescent whitening agents, enzymes andpigments, are sensitive to oxidants, and thus, may need to beco-dispensed in a separate liquid formulation. On the other hand, thereare encapsulation methods and other protective additives available forthese sensitive materials, such as, for example, from Coyne et al., U.S.Pat. Nos. 4,863,626, 5,093,021, and 5,225,102 and DeLeeuw et al., U.S.Pat. Nos. 5,254,287 and 5,167,854, incorporated herein by reference.

In some of the embodiments of this invention, such as when the deliveryexecution is a multiple delivery of liquid formulations, there may be aneed for a viscosity/phase modifier. Exemplary such materials includealkanolamines, especially triethanolamine, and a wide variety ofpolymers, including water soluble to water-miscible polymers, such aspolyethylene gycol, polyvinyl alcohol, polyvinyl acetate, polyacrylicacid, co-polymers of acrylic acid, co-polymers of methacrylic acid, andthe salts thereof. Other polymers include starch, xanthan gum, gumarabic and other naturally occurring polymers. Nonaqueous systems, onthe other hand, can be thickened with silicas, such as xerogels andfumed and precipitated silicas, such as Cab-O-Sil.

Anti-redeposition agents, such as carboxy methylcellulose, arepotentially desirable. Foam boosters, such as appropriate anionicsurfactants, may be appropriate for inclusion herein. Also, in the caseof excess foaming resulting from the use of certain surfactants,anti-foaming agents, such as alkylated polysiloxanes, e.g.dimethylpolysiloxane, would be desirable.

In certain hard surface cleaners, it is desirable to incorporate asource of particulate matter to act as abrasives. Abrasives aredesirable adjuncts for cleaning especially persistent stains. Abrasivescan be selected from a wide variety of particulate materials, including,but not limited to, calcium carbonate, glass beads, polymer beads,perlite, silica sand and various other insoluble, inorganic particulateabrasives are also possible, such as quartz, pumice, feldspar, tripoliand calcium phosphate. See Brodbeck et al., U.S. Pat. No. 5,529,711, andChoy et al., U.S. Pat. Nos. 5,554,321 and 5,470,499, all of which areincorporated herein by reference. Other types of abrasives include watersoluble materials present in an amount such as to exceed theirsolubility in water, leaving a portion thereof undissolved. These typesof materials include alkali metal bicarbonates, alkali metal phosphates,alkali metal borates, particularly sodium tetraborate decahydrate(borax) and pentahydrate (see U.S. patent application Ser. No.08/718,059, filed Sep. 17, 1996, entitled "Cleaner with Water SolubleAbrasive," incorporated herein by reference.).

7. Liquid Medium

So that the correct amount of active ingredients are dosed, theinventive compounds are combined with a liquid medium, most preferably,an inert, nonreactive liquid. Generally speaking, this nonreactiveliquid is principally water, or water combined with solvents, ornonaqueous solvents. For bench scale experiments, it is preferred to usedeionized water, although in the large scale manufacture of theinventive liquid compositions, this may not be necessary. The solventscan be chosen from any organic or inorganic solvents. Some preferredorganic solvents are those with a vapor pressure of at least 0.001 mm Hgat 25° C. and soluble to the extent of at least 1 g/100 ml water. Theorganic solvents used in the invention are preferably selected from C₁₋₆alkanol, C₃₋₂₄ alkylene glycol ether, and mixtures thereof. However,other, less water soluble or dispersible organic solvents may also beutilized. The alkanol can be selected from methanol, ethanol,n-propanol, isopropanol, butanol, pentanol, hexanol, their variouspositional isomers, and mixtures of the foregoing. It may also bepossible to utilize in addition to, or in place of, said alkanols, thediols such as methylene, ethylene, propylene and butylene glycols, andmixtures thereof. Other solvents, such as amines, ketones, ethers,esters, carboxylic acids, oils, hydrocarbons and halides may be usedalone, or mixtures thereof In the case of certain amines, e.g.,monoethanolamine, diethanolamine, etc., such solvents are alsoconsidered buffers (as described further above in 6). Thus, it ispossible that, in certain instances, these amines can be bifunctionalherein. Other examples of solvents can be found in Kirk-Othmer,Encyclopedia of Chemical Technology 3rd, Vol. 21, pp. 377-401 (1983),incorporated by reference herein. Where the formulation is a nonaqueousone, liquid nonionic surfactants, as previously mentioned, can be usedto provide the continuous phase. Additionally, an inorganic or organicacid, such as listed above in 5, could be used as the continuous phase.

8. Applications

a. Laundry Products

Compositions of the invention are useful as or in laundry products, suchas bleaching additives, detergents, detergent boosters, detergents withbleach, bleaches, bleaching aids, and stain removers. Among theadvantages derived from compositions of the invention are improvedcleaning, stain removal, spot removal, whitening, and brightening oftreated articles.

Further benefits from use of the inventive compositions includescavenging of free dye during laundering to prevent dye transfer betweengarments (sometimes known as dye transfer inhibition).

b. Surface Cleaners

Other product applications include household cleaning products, such ashard surface cleaners to be dissolved in water prior to use. Exemplarysurface cleaners are tile and grout cleaners, bathroom (floor, toilet,and counter) and kitchen (floor, sink, and counter) cleaners.Additionally, kitchen products such as dishwasher detergents with bleachor bleach cleaning and scrubbing pads are contemplated. Among thebenefits derived from use of the inventive compositions in suchapplications are improved stain and spot removal and general cleaning ofthe treated surfaces to remove food, rust, grime, mildew, mold, andother typical stains found on such surfaces.

In the hard surface cleaning area, the present invention has been foundto benefit from more acidic conditions (i.e., lower pH's) than forlaundry formulations. These pH's can be from about 0 to about 8, morepreferably between about 2 and 7.5 At these lower pH levels, the extentof bleaching--when the hard surface cleaner is formulated with both theMMA compound and a source of active oxygen--appears to become improved.

In one preferred embodiment of a hard surface cleaner delivery, as inthe laundry product formulation, a dual chambered container/dispenser ispreferred. One chamber contained an H₂ O₂ /MMA solution at an acidic pH.The other chamber contained agents to adjust the pH to the optimumlevel, namely, an alkaline buffer and optionally, a surfactant. Otheragents could be included for improved cleaning performance (thickeners,chelating agents, builders, etc.) or aesthetic appeal (dyes, colorants,fragrances). The preferred delivery is a trigger sprayer, which mustblend the two solutions/fluids from the two chambers prior to deliveringthe combined solutions as a spray. This could be accomplished by eithera mixing chamber, or by directing two fluid streams to a common targetpoint by means of a diverter or other redirection means. The surfactantor surfactants used in the other chamber could be selected from thediverse variety disclosed above in 4. Further, it is common to includein hard surface cleaners at least one solvent to further enhancecleaning performance and to disperse hydrophobic or poorly solublematerials into the liquid cleaner. Fragrances and colorants as providedfrom 6 are also desirable. Buffers selected from the variousacids/alkaline materials disclosed from 5 are desirable, as well asthickening agents which allow the blended liquids to cling to verticalsurfaces, such as colloids (clays, alumina, silica) or surfactants,surfactant/solvent mixtures, or polymers. The thickening effect may becreated in situ as the two liquid streams are blended at the nozzle orother delivery orifice, or pre-exist in thickened form. The molar ratioof active oxygen:MMA differs from its concentration in laundry productformulations in that a higher total amount is often present. Forexample, the molar ratio can range from about 100:1 to about 1:10, morepreferably about 10:1 to about 1:1, most preferably about 5:1 to about1:1 H₂ O₂ :MMA.

Additionally, non-household product applications are contemplated wherean effective level of active oxygen generated in situ to treat water isuseful. Illustrative of such applications are pool and spa additives, aswell as cleaners to remove stains on outdoor concrete, stucco, siding,wood and plastic surfaces.

The advantages of a liquid cleaning or laundry product are quiteevident. First, the MMA compounds are stable in hydrogen peroxide,allowing versatility in formulation. A single container or dual ormultiple container delivery can be formulated. Liquid cleaning andlaundering products appear to be greatly desired by consumers and it isadvisable for the product formulator to offer liquid products as analternative or preferred consumer product. In laundry products, theliquid product is desirable to prespot or target stains on soiledfabrics and garments.

Aspects of the invention will now be illustrated by the followingexamples. It will be understood that these examples are intended toillustrate, and not to limit, the invention.

EXPERIMENTAL Example 1

In general, N-quaternary acetonitrile compounds are readily preparedfrom N-acetonitrile precursors by employing selected alkyl halides andusing well-known synthetic approaches, such as are described byMenschutkir, Z. Physik Chem., 5, 589 (1890), and Z. Physik. Chem., 6, 41(1890); Abraham, Progr. Phys. Org. Chem., 11, 1 (1974); and Arnett, J.Am. Chem. Soc., 102, 5892 (1980). Further methods are depicted in Germanpatent application DE OS 44 312 12, published Mar. 7, 1996, and in theconcurrently filed and application Ser. No. 08/905,511, filed Aug. 4,1997, a continuation of then concurrently filed and application Ser. No.08/758,542, now abandoned, of inventors Ulrich Annen et al., entitled"Process for Preparing N-Alkyl Ammonium Acetonitrile Compounds" (JSSDocket No.: 0409.073US5') both of which are incorporated herein byreference.

Compounds having the Formula I structure have a saturated ring formed bya plurality of atoms, broadly ranging from 3 to 9, although preferablycontaining 6 atoms including the N₁ atom. Preparation of these compoundswill most conveniently start with a compound already having the formedring. For example, a number of preparations of inventive nitriteshereinafter described will begin with a morpholine (see, e.g., theFormula II structure). An example of three membered rings is aziridine,e.g., N-methylacetonitrile aziridinium; as an example of four memberedrings there is azetidine, e.g., N-ethyl-N-methylacetonitrileazetidinium; as an example of five membered rings there is pyrrolidine,e.g., N-butylacetonitrile pyrrolidinium; as an example of six memberedrings, in addition to morpholine, there is piperidine, e.g.,acetonitrile piperidinium; as an example of seven membered rings thereis homopiperidinium; as an example of eight membered rings there istropane, e.g., N-methylacetonitrile-8-azabicyclo[3.2.1]octane; and, asan example of nine membered rings there is octahydroindole, e.g.,N-methylacetonitrile octahydroindolinium.

More particularly, in the preferred method of preparation a suitableamine is reacted with a monoaldehyde or a dialdehyde in an aqueousmedium (Step A) followed by subsequent quaternization (Step B) with analkylating agent. In Step A, the reaction is preferably either in the pHrange from 8 through 14, or the pH value is maintained at not less than2 in Step B.

Thus, an amine with the formula ##STR9## is reacted as Step A with amonoaldehyde or a dialdehyde R⁶ -CHO or OHC-R⁵ -CHO, whereby R⁵ is achemical bond or a C₁ to C₆ alkylene bridge, or an oxyalkylene bridge,and R⁶ stands for H or C₁₋₂₀ alkyl, and with hydrogen cyanide or analkali metal cyanide in an aqueous medium. Step B is quaternization withan alkylating agent R¹ -X in an aqueous medium without isolating theintermediate product from Step A.

In Step A, cyanohydrins, e.g., formadehyde cyanohydrin, can be formed asby-products from the aldehyde, that is used, and hydrogen cyanide. Thesecyanohydrins do not react further with the alkylating agent in Step B sothat renewed breaking down of the cyanohydrins into aldehyde andhydrogen cyanide in the final product is possible.

Without the procedure in accordance with the invention, Step B usuallyproceeds in a such a way that, as a result of hydrolysis of the addedalkylating agent the pH value of the reaction mixture drifts off fromthe alkaline or neutral region into the strongly acidic region withincreasing reaction time. The protonation of the amine nitrogen atom ofthe glycinonitrile, that has not yet been quaternized, sets in--incompetition with the alkylation--starting from a certain pH value sothat, at the end of the addition of the alkylating agent, no furtherreaction of the glycinonitrile takes place. Non-quaternizedglycinonitrile in the final product can also represent an undesiredsource of hydrogen cyanide.

Step A generates especially good results if a pH range of 9 through 13or, especially, 10 through 12, is utilized. In this pH range, thecyanohydrin that is formed is present in an equilibrium with thealdehyde and the hydrogen cyanide so that the re-formed adducts canreact to completion with the amine to give glycinonitrile.

If one also uses an excess of amine that amounts to 2 through 20 mole %or, especially about 3 through 10 mole % or, most particularly of all,about 4 through 7 mole %, based on the quantity of the hydrogen cyanideor alkali metal cyanide that is used, then one achieves even moreextensive suppression of hydrogen cyanide and ancillary components, thatliberate hydrogen cyanide, in the final product.

Step B generates especially good results if the pH values are notreduced below 2.5 and, especially, not below 3. An optimum pH range forthe quaternization of Step B is 2.5 through 5 or, especially, 3 through4.

Use is also made of an excess of alkylating agent that amounts to 10 to40 mole % or, especially, 15 to 25 mole % based on the quantity of aminethat is used in Step A, then one achieves still more extensivesuppression of the hydrogen cyanide and the subsidiary components, thatliberate hydrogen cyanide, in the final product.

Once the nitrites are prepared in quaternized form, formation of thepreferred bisulfate or sulfate form preferably is by heating an alkylsulfate form, in an acid aqueous solution. For example, a suitableelevated temperature is about 40° C. to about 1 50° C.; more preferablyabout 70° C. to about 110° C. The acid aqueous solution may have a pH inthe range of about -1 to 6, more preferably from 0 to 3, with theheating being for a period of about 1 to 50 hours.

Aspects of the invention will now be illustrated by the followingexamples. It will be understood that these examples are intended toillustrate, and not to limit, the invention.

Example 2

Concentrated Laundry Additive Formulations

TABLE I discloses preferred, more preferred and most preferred rangesfor a concentrated laundry additive which would be within the scope ofthis invention:

                  TABLE I                                                         ______________________________________                                                    Preferred                                                                              More Preferred                                             Ingredient Range Range Most Preferred                                       ______________________________________                                        Anionic Surfactant                                                                        0-20%    0-10%       10.0%                                          Nonionic Surfactant 0-20% 0-10% 8.0%                                          Nonionic Ethoxylated 0-20% 0-10% 6.5%                                         Surfactant                                                                    Amphoteric Surfactant 0-20% 0-10% 1.5%                                        Hydrogen peroxide 1-10% 3-6%  6%                                              MMA Compound.sup.1 0.1-10%   1-8%  2%                                         Fluorescent Whitening 0-2%  0-1%  0.5%                                        Agent                                                                         Builder 0-10% 0-5%  1%                                                        Preservative  0-0.1%  0-0.1% 0.02%                                            Chelating Agent 0-5%  0-2%  2%                                                pH Adjusting Salt.sup.2 0-5%  0-2%  1%                                        Viscosity Modifier 0-10% 0.1-5%   3%                                          Dye/Colorant  0-0.5%  0-0.5% 0-0.5%                                           Fragrance  0-0.5%  0-0.5% 0-0.5%                                              Water 0-95% q.s. to 100% q.s. to 100%                                       ______________________________________                                         .sup.1 Inventive compound, preferably MMAMS, MMAS, MMABS or MMATS.            .sup.2 Can be either acid or alkali, depending on pH of formulation           resulting from other ingredients. In general, it is desirable to attain,      for optimal chemical storage stability, a final product pH from -1-5, mor     preferably 0-2 and most preferably 0-1. The acids and bases described in      5. above are utilized.                                                   

In the remaining examples, the same footnotes apply and will not berepeated.

In the next Example, a dual delivery system as discussed in 3, above, isdisclosed which would be within the invention.

Example 3

Two Part Concentrated Laundry Additive (Dual Chamber Bottle)

    ______________________________________                                                    Preferred                                                                              More Preferred                                             Ingredient Range Range Most Preferred                                       ______________________________________                                        Part A (1st Chamber)                                                            Anionic Surfactant                                                                          0-30%     0-20%    10.0%                                        Nonionic Surfactant 0-30%  0-20% 10.0%                                        Hydrogen Peroxide 1-10% 3-6% 6%                                               MMA 0.1-10%   1-8% 2%                                                         Preservative  0-0.1%   0-0.1% 0.02%                                           Chelating Agent 0-5%  0-2% 2%                                                 pH Adjusting Salt 0-5%  0-2% 1%                                               Dye/Colorant  0-0.5%   0-0.5% 0-0.5%                                          Water 0-95% q.s. to 100% q.s. to 100%                                       Part B (2nd Chamber)                                                            Nonionic Ethoxylated                                                                        0-30%     0-20%    6.5%                                         Surfactant                                                                    Amphoteric Surfactant 0-30%  0-20% 1.5%                                       Enzymes 0-5%  0-2% 1%                                                         Fluorescent Whitening 0-2%  0-1% 0.5%                                         Agent                                                                         Builder 0-10% 0-5% 1%                                                         pH Adjusting Salt 0-10% 0-5% 0.5%                                             Viscosity Modifier 0-10% 0-5% 3%                                              Dye/Colorant  0-0.5%   0-0.5% 0-0.5%                                          Fragrance  0-0.5%   0-0.5% 0-0.5%                                             Water 0-95% q.s. to 100% q.s. to 100%                                       ______________________________________                                    

In the above system, Part A and Part B would be stored in separatecompartments or chambers to prevent intermixing (cross-contamination orpremature reaction). At time of use, preferably equal proportions (or,in an alternative embodiment, in a fixed ratio) of Part A and Part Bwould be combined by the user (for example, by co-metering the twoliquid formulations) and poured into, for example, a washing apparatus.Ingredients would be placed into the appropriate Part A or Part B so asto achieve the optimum physical and chemical storage stability, andindividual ingredient stability. Additionally, by separate storage in amultiple delivery system, oxidation-sensitive materials, such asalkaline proteases, could be stored in an alkaline environment, whilethe acid-stable ingredients, such as hydrogen peroxide and the MMAcompounds, could be stored in an acidic environment. Finally, as the MMAcompound/hydrogen peroxide combination works best in an alkalineenvironment, upon dispensing into the alkaline wash water, the bestperformance conditions would be achieved upon such dispensing.

In the next Example, a preferred concentrated laundry additiveformulation is disclosed which is within the scope of the invention.

Example 4

Concentrated Laundry Additive

    ______________________________________                                        Ingredient   Wt. % Active                                                                              Commercial Material                                  ______________________________________                                        Anionic Surfactant                                                                         8%          C.sub.12-15 Alkylbenzene                                 Sulfonate                                                                   Nonionic Surfactant 5% Neodol 25-7                                            Hydrogen Peroxide 5% Cosmetic Grade Peroxide                                  MMA Compound 3.5%   MMAMS*                                                    Fluorescent Whitening 0.2%   Tinopal CBS-X                                    Agent                                                                         Builder 0.5%   Sodium Chloride                                                Preservative 0.02%   Butylated Hydroxytoluene                                 Chelating Agent 2% Dequest 2010                                               pH Adjusting Agent 1% Sulfuric Acid                                           Viscosity/Phase Modifier 1% Triethanolamine                                   Dye 0-0.5% Various Vendors                                                    Fragrance 0-0.5% "                                                            D.I. Water q.s.                                                             ______________________________________                                         *Not a presently commercially available material.                        

In the next Example, an especially preferred two part concentratedlaundry additive is disclosed which is within the invention.

Example 5

Two Part Concentrated Laundry Additive

    ______________________________________                                        Ingredient  Wt. %      Commercial Material                                    ______________________________________                                        Part A                                                                          Anionic Surfactant                                                                          10.0%      C.sub.12-15 Alkylbenzene Sulfonate                   Nonionic Surfactant 8.0% Neodol 25-12                                         Hydrogen Peroxide 6.0% Cosmetic Grade                                         MMA 2.0% MMAMS                                                                Preservative 0.2% Butylated Hydroxytoluene                                    Chelating Agent   2% Dequest 2006                                             pH Adjusting Salt   1% Phosphoric Acid                                        Dye/Colorant 0-0.5% Various Vendors                                           Water q.s. to 100%                                                          Part B                                                                          Nonionic Ethoxylated                                                                        6.5%       Neodol 25-7                                          Surfactant                                                                    Nonionic Surfactant 1.5% Barlox 12                                            Enzymes   1% Novo Protease                                                    Fluorescent Whitening 0.5% Tinopal AMS                                        Agent                                                                         Builder 1.0% Sodium Chloride                                                  pH Adjusting Salt 0.5% Sodium Hydroxide                                       Viscosity Modifier   3% Polyethylene Glycol                                   Dye/Colorant 0-0.5% Various Vendors                                           Fragrance 0-0.5% Various Vendors                                              Water q.s. to 100%                                                          ______________________________________                                    

In Examples 6-8 below, exemplary dual chamber hard surface cleanerformulations were created and tested for stain removal performanceagainst a laboratory mildew stain (Aspergillus niger). The stain wasapplied to bisque tiles (unglazed ceramic tiles to essentially mimicbathroom grout). A proprietary Minolta colorimeter was used to determinecleaning performance. To calibrate the calorimeter, a clean tile wasused, and then the stained tile was read. Then, after the inventivecleaning composition was applied, the colorimeter read the tiles, andthe readout would indicate % stain removal at various elapsed timeintervals. In the Examples, the pH level was varied to compareperformance at differing pH levels. Part A contained the MMA compound,hydrogen peroxide and a buffer. Part B contained an alkaline material.

Examples 6-8

    __________________________________________________________________________                  Example 6   Example 7   Example 8                               Ingredient    A   B   Blend                                                                             A   B   Blend                                                                             A   B   Blend                           __________________________________________________________________________    H.sub.2 O.sub.2                                                                             4.04    2.02                                                                              4.04    2.02                                                                              4.04    2.02                              MMAMS 10  5 10  5 10  5                                                       H.sub.2 SO.sub.4 2.43  1.21 0.89  0.45 0.89  0.45                             NaOH        1 0.5                                                             Na.sub.2 CO.sub.3  10 5  10 5  10 5                                           H.sub.2 O balance balance balance balance balance balance balance                                                         balance balance                 pH            7.6         8.5         9.5                                       Molar Ratio of H.sub.2 O.sub.2 : MMAMS 3 3 3                                __________________________________________________________________________

The formulations of Examples 6-8 were tested for performance in stainremoval as described above. It was found that, at lower pH's, theformulation--at equal dosages of active, i.e., at a 3:1 molar ratio ofH₂ O₂ :MMAMS--had better stain removal performance at lower pH. This isgraphically depicted in FIG. 1, in which the Y axis is % stain removal,the X axis is time in seconds. The data depicted have been adjusted for100% stain removal by focusing on the area where the inventive bleachingformulation was applied.

It is to be understood that while the invention has been described abovein conjunction with preferred specific embodiments, the description andexamples are intended to illustrate and not limit the scope of theinvention, which is defined by the appended claims.

We claim:
 1. A liquid cleaning composition including a compound with thestructure of Formula I ##STR10## wherein A is a saturated ring formed byfive atoms in addition to the N₁ atom, the five saturated ring atomsbeing four carbon atoms and a heteroatom, the substituent R₁ bound tothe N₁ atom of the Formula I structure is (a) a C₁₋₈ alkyl oralkoxylated alkyl where the alkoxy is C₂₋₄, (b) a C₄₋₂₄ cycloalkyl, (c)a C₇₋₂₄ alkylaryl, (d) a repeating or nonrepeating alkoxy or alkoxylatedalcohol, where the alkoxy unit is C₂₋₄, or (e) --CR_(2') R_(3') C=.tbd.Nwhere R_(2') and R_(3') are each H, a C₁₋₂₄ alkyl, cycloalkyl, oralkylaryl, or a repeating or nonrepeating alkoxyl or alkoxylated alcoholwhere the alkoxy unit is C₂₋₄, the R₂ and R₃ substituents are each H, aC₁₋₂₄ alkyl, cycloalkyl, or alkylaryl, or a repeating or nonrepeatingalkoxyl or alkoxylated alcohol where the alkoxy unit is C₂₋₄, andwherein Y is an counterion and Z is in the range of 0 to
 10. 2. Theliquid composition of claim 1 wherein the counterion is eitheralkylsulfate, bisulfate, sulfate, tosylate or mixtures thereof.
 3. Theliquid composition of claim 1 wherein said liquid includes an inert,nonreactive liquid.
 4. The liquid composition of claim 3 wherein saidliquid is selected from the group consisting of water, organic solventsand mixtures thereof.
 5. The liquid composition of claim 1 wherein saidliquid comprises a nonaqueous liquid.
 6. The liquid composition of claim5 wherein said nonaqueous liquid comprises liquid nonionic surfactants,organic solvents, or mixtures thereof.
 7. The liquid compositions ofclaim 1 wherein R₁ is a C₁₋₄ alkyl.
 8. The liquid composition of claim 7wherein R₁ is methyl.
 9. The liquid composition of claim 8 wherein R₂and R₃ are both hydrogen.
 10. The liquid composition of claim 9 whereinthe heteroatom is oxygen or sulphur.
 11. The liquid composition of claim10 wherein the heteroatom is oxygen.